This invention relates to new metal complex pigments, processes for producing them and their use.
EP-A-73 463 discloses coloristically valuable pigments. These still have application disadvantages, however. In particular, strong lightfast red pigments are not disclosed therein.
It is accordingly an object of the present invention to provide new pigments which are free of the above-described disadvantages.
The invention accordingly provides metal complexes of an azo compound which conforms to the formula (I) or one of its tautomeric structures 
wherein
R and Rxe2x80x2 are independently OH, NH2, NHxe2x80x94CN, arylamino or acylamino,
R1 and R1xe2x80x2 are independently xe2x80x94H or xe2x80x94NH2,
and which contain at least one guest compound,
characterized in that the metal complexes correspond to the mono-, di-, tri- and tetraanions of the azo compounds of the formula (I) with the metals selected from the group consisting of Ca, Zn, Cu, Fe, Co, Sr, Ba, Cr, Sn, Al, Mg, Cd, Pb and La.
Aryl substituents in the formula (I) are preferably phenyl or naphthyl, which may each be substituted for example by halogen such as F, Cl, Br, xe2x80x94OH, C1-C6-alkyl, C1-C6-alkoxy, xe2x80x94NH2, xe2x80x94NO2 and xe2x80x94CN.
Acyl substituents in the formula (I) are preferably (C1-C6-alkyl)-carbonyl, phenylcarbonyl, C1-C6-alkylsulphonyl, phenylsulphonyl, optionally C1-C6-alkyl-, phenyl- and naphthyl-substituted carbamoyl, optionally C1-C6-alkyl-, phenyl- and naphthyl-substituted sulphamoyl or optionally C1-C6-alkyl-, phenyl- or naphthyl-substituted guanyl, where the alkyl radicals mentioned may be substituted for example by halogen such as Cl, Br, F, xe2x80x94H, xe2x80x94CN, xe2x80x94NH2 or C1-C6-alkoxy and the phenyl and naphthyl radicals mentioned may be substituted for example by halogen such as F, Cl, Br, xe2x80x94H, C1-C6-alkyl, C1-C6-alkoxy, xe2x80x94NH2, xe2x80x94NO2 and xe2x80x94CN.
The term xe2x80x9cmetal complexesxe2x80x9d is herein also to be understood as meaning metal salts.
Very particularly preferred metal complexes are those of azo compounds of the formula (I) which in the form of their free acid conform to one of its tautomeric structures of the formula (II) 
where
R and Rxe2x80x2 are independently selected from the group consisting of OH and NHCN,
and include at least one other compound.
Preference is given here in particular to organic metal complexes of those azo compounds of the formula (II) which in the form of their free acid correspond to one of the tautomeric structures of the formulae (IIa to IIc) 
Particularly preferably, the compounds of the formula (I) are the 1:1 azo metal complexes which conform to the formula (Ia) or one of its tautomeric forms 
wherein
Me corresponds to one of the above-mentioned metal centres,
R and Rxe2x80x2 are each as defined above, and
R1 and R1xe2x80x2 are independently=O or xe2x80x94NH.
In general, the metal complex compound forms a layered crystal lattice in which the bonding within a layer is essentially via hydrogen bonds and/or metal ions. Preferably, the metal complex compounds are metal compounds which form a crystal lattice which consists of essentially planar layers.
The metal complexes hosting other guest compounds can be present in the form of inclusion compounds, intercalation compounds and also as solid solutions.
Useful metal complexes also include metal complexes in which a metal-containing compound, for example a salt or metal complex, is incorporated into the crystal lattice of the metal complex. In this case, in the formula (I), a portion of the metal may be replaced by other metal ions, or further metal ions can enter into a more or less pronounced interaction with the metal complex.
Included compounds may be organic compounds and inorganic compounds. Compounds which can be included come from a very wide variety of classes of compounds. For purely practical reasons, preference is given to such compounds as are liquid or solid under normal conditions (25xc2x0 C., 1 bar).
Of the liquid substances, preference is given in turn to those which have a boiling point (1 bar) of 100xc2x0 C. or higher, preferably of 150xc2x0 C. and higher. Suitable compounds are preferably acyclic and cyclic organic compounds, for example aliphatic and aromatic hydrocarbons, which may be substituted. for example by OH, COOH, NH2, substituted NH2, CONH2, substituted CONH2, SO2NH2, substituted SO2NH2, SO3H, halogen, NO2, CN, xe2x80x94SO2-alkyl, xe2x80x94SO2-aryl, xe2x80x94O-alkyl, xe2x80x94O-aryl, xe2x80x94O-acyl.
Aryl substituents are preferably phenyl or naphthyl, which may each be substituted for example by halogen such as F, Cl, Br, xe2x80x94H, C1-C6-alkyl, C1-C6-alkoxy, xe2x80x94NH2, xe2x80x94NO and xe2x80x94CN.
Alkyl substituents are preferably C1-C6-alkyl, which may be substituted for example by halogen, such as chlorine, bromine, fluorine, xe2x80x94OH, xe2x80x94CN, xe2x80x94NH2 or C1-C6-alkoxy.
Cycloalkyl substituents are preferably C3-C7-cycloalkyl, especially C5-C6-cycloalkyl, which may be substituted for example by C1-C6-alkyl, C1-C6-alkoxy, halogen such as Cl, Br, F, C1-C6-alkoxy, xe2x80x94OH, xe2x80x94CN and NH2.
Aralkyl substituents are preferably phenyl- or naphthyl-C1-C4-alkyl, which may be substituted in the aromatic radicals by halogen such as F, Cl, Br, xe2x80x94OH, C1-C6-alkyl, C1-C6-alkoxy, xe2x80x94NH2, xe2x80x94NO2 and xe2x80x94CN, for example.
Acyl substituents are preferably (C1-C6-alkyl)-carbonyl, phenylcarbonyl, C1-C6-alkylsulphonyl, phenylsulphonyl, optionally C1-C6-alkyl-, phenyl- and naphthyl-substituted carbamoyl, optionally C1-C6-alkyl-, phenyl- and naphthyl-substituted sulphamoyl or optionally C1-C6-alkyl-, phenyl- or naphthyl-substituted guanyl, where the alkyl radicals mentioned may be substituted for example by halogen such as Cl, Br, F, xe2x80x94OH, xe2x80x94CN, xe2x80x94NH2 or C1-C6-alkoxy and the phenyl and naphthyl radicals mentioned may be substituted for example by halogen such as F, Cl, Br, xe2x80x94OH, C1-C6-alkyl, C1-C6-alkoxy, xe2x80x94NH2, xe2x80x94NO2 and xe2x80x94CN.
Specific examples are paraffins and paraffin oils; triisobutylene, tetraisobutylene, mixtures of aliphatic and aromatic hydrocarbons as produced in petroleum fractionation for example; chlorinated paraffin hydrocarbons such as dodecyl chloride or stearyl chloride; C10-C30-alcohols such as 1-decanol, 1-dodecanol, 1-hexadecanol, 1-octadecanol and their mixtures, olein alcohol, 1,12-octadecanediol, fatty acids and their salts and mixtures, for example formic acid, acetic acid, dodecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, fatty acid esters, for example the methyl esters of C10-C20-fatty acids, fatty acid amides, such as stearamide, stearic acid monoethanolamide, stearic acid diethanolamide, stearonitrile, fatty amines, for example dodecylamine, cetylamine, hexadecylamine, octadecylamine and others; salts of fatty amines with sulphonic and carboxylic acids, isocyclic hydrocarbons such as cyclododecane, decahydronaphthalene, o-, m-, p-xylene, mesitylene, dodecylbenzene mixture, tetralin, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, biphenyl, diphenylmethane, acenaphthene, fluorene, anthracene, phenanthrene, m-, p-terphenyl, o-, p-dichlorobenzene, nitrobenzene, 1-chloronaphthalene, 2-chloronaphthalene, 1-nitronaphthalene, isocyclic alcohols and phenols and their derivatives such as benzyl alcohol, decahydro-2-naphthol, diphenyl ether, sulphones, for example diphenyl sulphone, methyl phenyl sulphone, 4,4xe2x80x2-bis-2-(hydroxyethoxy)diphenyl sulphone; isocyclic carboxylic acids and their derivatives such as be,nzoic acid, 3-nitrobenzoic acid, cinnamic acid, 1-naphthalenecarboxylic acid, phthalic acid, dibutyl phthalate, dioctyl phthalate, tetrachlorophthalic acid, 2-nitrobenzamide, 3-nitrobenzamide, 4-nitrobenzamide, 4-chlorobenzamide, sulphonic acids, such as 2,5-dichlorobenzenesulphonic acid, 3-nitro-, 4-nitro-benzenesulphonic acid, 2,4-dimethylbenzenesulphollic acid, 1- and 2-naphthalenesulphonic acid, 5-nitro-1- and 5-nitro-2-naphthalenesulphonic acid, di-sec-butylnaphthalenesulphonic acid mixture, biphenyl-4-sulphonic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalenedisulphonic acid, 3-nitro-1,5-naphthalenedisulphonic acid, 1-anthraquinonesulphonic acid, 2-anthraquinonesulphonic acid, biphenyl-4,4xe2x80x2-disulphonic acid, 1,3,6-naphlhalenetrisulphonic acid and the salts of these sulphonic acids e.g. the sodium, potassium, calcium, zinc, nickel and copper salts; sulphonamides such as benzenesulphonamide, 2-, 3- and 4-nitrobenzenesulphonamide, 2-, 3- and 4-chlorobenzenesulphonamide, 4-methoxybenzeniesulphonamide, 3,3xe2x80x2-sulphonylbisbenzenesulphonamide, 4,4xe2x80x2-oxybisbenzenesulphonamide, 1- and 2-naphthalenesulphonic.
Carboxamides and sulphonamides are a preferred group of compounds to be included, also suitable in particular are urea and substituted ureas such as phenylurea, dodecylurea and others and also their polycondensates with aldehydes, especially formaldehyde; heterocycles such as barbituric acid, benzimidazolone, 5-benzimidazolonesulphonic acid, 2,3-dihydroxyquinoxaline, 2,3-dihydroxyquinoxaline-6-sulphonic acid, carbazole, carbazole-3,6-disulphonic acid, 2-hydroxyquinoline, 2,4-dihydroxyquinoline, caprolactam, melamine, 6-phenyl-1,3,5-triazine-2,4-diamine, 6-methyl-1,3,5-triazine-2,4-diamine, cyanuric acid.
Preferred metal complexes contain included surface-active compounds, especially surfactants, which are known for example from K. Lindner, Tenside-Textilhilfsmittel-Waschrohstoffe, 2nd edition, Volume I, Wissenschaftliche Verlagsgesellschaft mbH, Stuttgart, 1964. They can be anionic, non-ionic or cationic compounds or ampholytes. Examples of suitable anionic compounds are true soaps, salts of aminocarboxylic acids, salts of lower or higher acylated aminocarboxylic acids, fatty acid sulphates, sulphates of fatty acid esters, amides etc., primary alkyl sulphates, sulphates of oxo alcohols, secondary alkyl sulphates, sulphates of esterified or etherified polyoxy compounds, sulphates of substituted polyglycol ethers (sulphated ethylene oxide adducts), sulphates of acylated or alkylated alkanolamines, sulphonates of fatty acids, their esters, amides, etc., primary alkyl sulphonates, secondary alkyl sulphonates, alkyl sulphonates with acyls attached in ester fashion, alkyl or alkylphenyl ether sulphonates, sulphonates of polycarboxylic esters, alkylbenzenesulphonates, alkylnaphthalenesulphonates, fatty aromatic sulphonates, alkylbenzimidazolesulphonates, phosphates, polyphosphates, phosphonates, phosphinates, thiosulphates, hydrosulphites, sulphinates, persulphates. Examples of suitable non-ionic compounds are esters and ethers of polyalcohols, alkyl polyglycol ethers, acyl polyglycol ethers, alkylaryl polyglycol ethers, acylated and alkylated alkanolamine polyglycol ethers. Examples of suitable cationic compounds are alkylamine salts, quaternary ammonium salts, alkylpyridinium salts, simple and quaternary imidazoline salts, alkyldiamines and alkylpolyamines, acyldiamines and acylpolyamines, acylalkanolamines, alkanolamine esters, alkyl-OCH2xe2x80x94N-pyridinium salts, alkyl-COxe2x80x94NHxe2x80x94CH2xe2x80x94N-pyridinium salts, alkylethyleneureas, sulphonium compounds, phosphonium compounds, arsenium compounds, alkylguanidines, acylbiguanidides. Examples of suitable ampholytes are alkylbetaines, sulphobetaines and aminocarboxylic acids. Preference is given to using non-ionic surfactants, especially the ethylene oxide addition products of fatty alcohols, fatty amines and also of octyl- or nonylphenol.
A further important group of guest compounds are natural resins and resin acids such as for example abietic acid and its conversion products and salts. Examples of such conversion products are hydrogenated, dehydrogenated and disproportionated abietic acids. These can further be dimerized, polymerized or modified by addition of maleic anhydride and fumaric acid. Also of interest are the resin acids modified at the carboxyl group such as for example the methyl, hydroxyethyl, glycol, glyceryl and pentaerythritol esters and also resin acid nitrites and resin acid amines and also dehydroabietyl alcohol.
Also suitable for inclusion are polymers, preferably water-soluble polymers, for example ethylene-propylene oxide block polymers, preferably having an Mn not less than 1000, especially of 1000 to 10,000 g/mol, polyvinyl alcohol, poly(meth)-acrylic acids, modified cellulose, such as carboxymethylcelluloses. hydroxyethyl- and xe2x80x94propylcelluloses, methyl- and ethyl-hydroxyethylcelluloses.
Other suitable guest compounds are condensation products based on
A) sulphonated aromatics,
B) aldehydes and/or ketones and optionally
C) one or more compounds selected from the group of the non-sulphonated aromatics, urea and urea derivatives.
Based on means that the condensation product was optionally prepared from other reactants besides A, B and optionally C. Preferably, however, the condensation products for the purposes of this invention are prepared only from A, B and optionally C.
The sulphonated aromatics of component A) will be understood in the context of this invention as including sulphomethylated aromatics as well. Preferred sulphonated aromatics are naphthalenesulphonic acids, phenolsulphonic acids, dihydroxybenzenesulphonic acids, sulphonated ditolyl ethers, sulphomethylated 4,4xe2x80x2-dihydroxydiphenyl sulphone, sulphonated diphenylmethane, sulphonated biphenyl, sulphonated hydroxybiphenyl, especially 2-hydroxybiphenyl, sulphonated terphenyl or benzenesulphonic acids.
Aldehydes and/or ketones useful as component B) include in particular aliphatic, cycloaliphatic and also aromatic ones. Preference is given to aliphatic aldehydes, particularly preferably formaldehyde and other aliphatic aldehydes of 3 to 5 carbon atoms.
Examples of non-sulphonated aromatics useful as component C) are phenol, cresol, 4,4xe2x80x2-dihydroxydiphenyl sulphone and dihydroxydiphenylmethane.
Examples of urea derivatives are dimethylolurea, alkylureas, melamine and guanidine.
Preference is given to a condensation product based on
A) at least one sulphonated aromatic selected from the group consisting of naphthalenesulphonic acids, phenolsulphonic acids, dihydroxybenzenesulphonic acids, sulphonated ditolyl ethers, sulphomethylated 4,4xe2x80x2-dihydroxydiphenyl sulphone, sulphonated diphenylmethane, sulphonated biphenyl, sulphonated hydroxybiphenyl, especially 2-hydroxybiphenyl, sulphonated terphenyl and benzenesulphonic acids,
B) formaldehyde and optionally
C) one or more compounds selected from the group consisting of phenol, cresol, 4,4xe2x80x2-dihydroxydiphenyl sulphone, dihydroxydiphenylmethane, urea, dimethylolurea, melamine and guanidine.
Preferred condensation products are condensation products based on 4,4xe2x80x2-dihydroxydiphenyl sulphone, sulphonated ditolyl ether and formaldehyde; 4,4xe2x80x2-dihydroxydiphenyl sulphone, phenolsulphonic acid and formaldehyde; 4,4xe2x80x2-dihydroxydiphenyl sulphone, sodium bisulphite, formaldehyde and urea; naphthalenesulphonic acid, 4,4xe2x80x2-dihydroxydiphenyl sulphone and formaldehyde; sulphonated terphenyl and formaldehyde; and/or sulphonated 2-hydroxybiphenyl and formaldehyde and also naphthalenesulphonic acid and formaldehyde.
Particular preference for use as guest compounds is given to melamine or melamine derivatives, especially those of the formula (III) 
where
R6 is hydrogen or C1-C4-alkyl, which is optionally substituted by OH groups, very particularly preferably where
R6 is hydrogen.
The amount of substance which can be incorporated as guest compounds in the crystal lattice of the metal complex is generally 5% to 200% by weight, based on the amount of host compound. Preference is given to a guest compound amount of 10 to 100% by weight. The amount referred to here is the amount of substance which is not washed out by suitable solvents and which is obtained from the elemental analysis. Naturally, it is also possible to add more or less than the aforementioned amount of substance, and it may be optionally dispensed with to wash an excess out. Preference is given to amounts of 10 to 150% by weight.
The preferred inventive metal complexes of the azo compounds of the formula (I) which contain another compound as guest compound have a colour locus which is defined by the following ranges for the chromaticity coordinates x and y:
The colour loci are determined on alkyd-melamine varnishes according to DIN 53 238 in which the pigments are present in a completely dispersed state.
x=0.38 to 0.72, preferably 0.4 to 0.7
y=0.14 to 0.36, preferably 0.17 to 0.35
where       x    =                            X                      X            +            Y            +            Z                          ⁢                  xe2x80x83                ⁢        y            =              Y                  X          +          Y          +          Z                      ,
where
X, Y and Z are tristimulus values.
The standardized colour system is described in Bayer Farben Revue, Sonderheft 3/2 D, 1986; p. 12-14.
Inclusion compounds, intercalation compounds and solid solutions of metal complexes per se are known from the literature. They and their preparation are described for example in EP 0 074 515 and EP 0 073 463.
The preparation of these compounds can be effected analogously to that described for example in EP 0 073 464. The invention further provides a process for preparing the inventive metal complexes, which is characterized in that the azo compound of the formula (I), preferably in the form of an alkali metal salt such as Na, Li or K salt, is reacted with a metal salt of metals selected from the group consisting of Ca, Zn, Cu, Fe, Co, Sr, Ba, Cr, Sn, Al, Mg, Cd, Pd and La, preferably at pH less than 7, and the resultant metal complex is reacted with the compound to be included as guest compound, preferably at a pH of 1 to 7. A preferred embodiment of the process of the invention is characterized in that, following the reaction with the guest compound, the pH is raised to 4.5 or higher, preferably to 4.5 to 7, if the reaction with the guest compound took place at pH of less than 4.5.
The metal salt is preferably selected from water-soluble metal salts of the abovementioned metals, especially chlorides, bromides, acetates, nitrates, etc. Preferred metal salts have a water solubility of more than 20 g/l, especially more than 50 g/l, at 20xc2x0 C.
Suitable metal salts for preparing the salts and complexes of the azo compounds are for example magnesium chloride, magnesium sulphate, calcium chloride, calcium acetate, calcium formate, barium chloride, barium nitrate, barium acetate, barium carbonate, strontium nitrate, manganese chloride, manganese sulphate, iron(III) chloride, iron(III) nitrate, iron(II) sulphate, cobalt chloride, cobalt nitrate, cobalt sulphate, aluminium sulphate, aluminium nitrate, chromium(III) sulphate, chromium(III) nitrate, zinc chloride, zinc sulphate, zinc acetate, cadmium chloride, cadmium sulphate, cadmium nitrate, copper(II) sulphate, copper(II) chloride, copper(II) acetate and copper(II) formate, lanthanum nitrate and aluminium chloride hydrate.
It is also possible to use mixtures of these salts, which may also contain various ones of the metals mentioned. The use of such salt mixtures is especially advisable to obtain intermediate hues for the coloured end products.
The thusly obtained metal complexes according to the invention can then be isolated in the form of aqueous press cakes by filtration of their aqueous suspensions. These press cakes can be dried according to customary drying processes, for example after washing with hot water.
Useful drying processes include for example paddle drying or spray drying of appropriately aqueous slurries.
The pigment can subsequently be afterground.
If the metal complexes according to the invention are too harsh in texture, they can be converted into soft-textured pigments, for example by the method described in DE 19 847 586.
The aqueous press cake is preferably spray-dried as an aqueous slurry, the slurry preferably containing ammonia and/or an inorganic or organic base.
It is likewise preferable for the metal complexes of the invention, if they have a dispersing harshness of  greater than 250, to be heat-treated in the presence of water and optionally organic solvents either at a pH of 1 to 4, preferably 1 to 3, especially 1.5 to 2.5, or at a pH of 9 to 13, preferably 10 to 11, and at a temperature of 80 to 180xc2x0 C., preferably 90 to 140xc2x0 C., especially 95 to 110xc2x0 C.
The heat treatment is preferably complete when the metal complex of the invention, which contains a guest compound, has a dispersing harshness of less than 250.
The invention therefore also provides for the inventive metal complexes having a dispersing harshness of less than 250 (measured on the lines of DIN 53 775 Part 7), the cold rolling temperature being 25xc2x0 C. and the hot rolling temperature 150xc2x0 C.
All the dispersing harshnesses reported herein were determined by this modified method.
The metal complexes of an azo compound of the formula (I) which contain at least one guest compound are herein referred to as pigments. The invention therefore also provides for pigment preparations comprising at least a pigment according to the invention and a dispersant.
Dispersants for the purposes of the present invention are substances which stabilize the pigment particles in their fine particulate form in aqueous media. Finely particulate is preferably understood as meaning a fine division of 0.001 to 5 xcexcm, especially of 0.005 to 1 xcexcm, particularly preferably of 0.005 to 0.5 xcexcm.
The pigment preparations are preferably solid preparations, which are present in pulverulent or granular form.
Suitable dispersants are for example anionic, cationic, amphoteric or non-ionic.
Suitable anionic dispersants are in particular condensation products of aromatic sulphonic acids with formaldehyde, such as condensation products of formaldehyde and alkylnaphthalenesulphonic acids or of formaldehyde, naphthalenesulphonic acids and/or benzenesulphonic acids, condensation products of optionally substituted phenol with formaldehyde and sodium bisulphite. Also suitable are dispersants from the group of the sulphosuccinic esters and alkylbenzenesulphonates. Also sulphated, alkoxylated fatty acid alcohols or salts thereof. Alkoxylated fatty acid alcohols are to be understood as meaning in particular those C6-C22 fatty acid alcohols which are provided with 5 to 120, preferably 5 to 60, especially with 5 to 30, ethylene oxide and are saturated or unsaturated, especially stearyl alcohol. Particular preference is given to a stearyl alcohol alkoxylated with 8 to 10 ethylene oxide units. The sulphated alkoxylated fatty acid alcohols are preferably present as salts, especially as alkali metal or amine salts, preferably as diethylamine salt. Also suitable in particular are ligninsulphonates, for example those which are obtained by the sulphite or kraft process. Preferably they are products which are partially hydrolyzed, oxidized, propoxylated, sulphonated, sulphomethylated or desulphonated and fractionated according to known processes, for example according to the molecular weight or according to the degree of sulphonation. Mixtures of sulphite and kraft ligninsulphonates are likewise very effective. Of particular suitability are ligninsulphonates having an average molecular weight between 1000 and 100,000, an active ligninsulphonate content of not less than 80% and preferably a low level of polyvalent cations. The degree of sulphonation can vary widely.
Examples of useful non-ionic dispersants are reaction products of alkylene oxides with alkylatable compounds, for example fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, arylalkylphenols, such as styrene-phenol condensates, carboxamides and resin acids. They are for example ethylene oxide adducts from the class of the reaction products of ethylene oxide with:
a1) saturated and/or unsaturated fatty alcohols of 6 to 22 carbon atoms or
b1) alkylphenols having 4 to 12 carbon atoms in the alkyl radical or
c1) saturated and/or unsaturated fatty amines of 14 to 20 carbon atoms or
d1) saturated and/or unsaturated fatty acids of 14 to 20 carbon atoms or
e1) hydrogenated and/or unhydrogenated resin acids.
Suitable ethylene oxide adducts are in particular the alkylatable compounds mentioned under a1) to e1) when combined with 5 to 120, especially 5 to 100, especially 5 to 60, particularly preferably 5 to 30, mol of ethylene oxide.
Suitable dispersants also include the esters of the alkoxylation product of the formula (X) known from DE-A 19 712 486, which has an earlier priority date, or from DE-A 19 535 246, which conform to the formula (XI) and also these optionally mixed together with the parent compounds of the formula (X). The alkoxylation product of a styrene-phenol condensate of the formula (X) is as hereinbelow defined: 
where
R15 is hydrogen or C1-C4-alkyl,
R16 is hydrogen or CH3,
R17 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or phenyl,
m is from 1 to 4,
n is from 6 to 120,
R18 is identical or different for each unit with the index n and represents hydrogen, CH3 or phenyl subject to the proviso that, in the case of CH3 being present in the various xe2x80x94(xe2x80x94CH2xe2x80x94CH(R18)xe2x80x94Oxe2x80x94) groups, R18 is CH3 in 0 to 60% of the total value of n and is hydrogen in 100 to 40% of the total value of n and in the case of phenyl being present in the various xe2x80x94(xe2x80x94CH2xe2x80x94CH(R18)xe2x80x94Oxe2x80x94) groups, R18 is phenyl in 0 to 40% of the total value of n and is hydrogen in 100 to 60% of the total value of n.
Esters of alkoxylation products (X) conform to the formula (XI) 
where
R15xe2x80x2, R16xe2x80x2, R17xe2x80x2, R18xe2x80x2, mxe2x80x2 and nxe2x80x2 assume the scope of meaning of R15, R16, R17, R18, m and n, respectively, but independently thereof,
X is xe2x80x94SO3, xe2x80x94SO2, xe2x80x94PO3 or xe2x80x94COxe2x80x94(R19)xe2x80x94COO,
Kat is a cation selected from the group consisting of H+, Li+, Na+, K+, NH4+ and HOxe2x80x94CH2CH2xe2x80x94NH3+, subject to the proviso that in the case of X=xe2x80x94PO3xe2x88x92 two cations are present, and
R19 is a divalent aliphatic or aromatic radical, preferably C1-C4-alkylene, especially ethylene, monounsaturated C2-C4 radicals, especially acetylene, or optionally substituted phenylene, especially ortho-phenylene, preferred substituents being C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or phenyl.
Specific individual compounds of the formula (XI) are known for example from DE-A-19 712 486 and mixtures of the formulae (X) and (XI) for example from DE-A-19 535 256, which each form part of this application.
A preferred dispersant is the compound of the formula (XI). Preferably a compound of the formula (XI) where X is a radical of the formula xe2x80x94COxe2x80x94(R19)xe2x80x94COOxe2x80x94 and R19 is as defined above.
Preference for use as dispersant is likewise given to a compound of the formula (XI) used together with a compound of the formula (X). In this case, the dispersant preferably contains 5 to 99% by weight of the compound (XI) and 1 to 95% by weight of the compound (X).
Polymeric dispersants are for example water-soluble and also water-emulsifiable compounds, for example homo- and copolymers such as random or block copolymers.
Particularly preferred polymeric dispersants are for example AB, BAB and ABC block copolymers. In the AB or BAB block copolymers, the A segment is a hydrophobic homopolymer or copolymer which provides a bond to the pigment and the B block is a hydrophilic homopolymer or copolymer or a salt thereof and ensures dispersal of the pigment in an aqueous medium. Such polymeric dispersants and their synthesis are known for example from EP-A-518 225 and EP-A-556 649.
The dispersant is preferably used in an amount of 0.1 to 100% by weight, especially 0.5 to 60% by weight, based on the use level of pigment in the pigment preparation.
The preparation may contain further additives, of course. For instance, additives which reduce the viscosity of an aqueous suspension and increase the solids content, such as the abovementioned carboxamides and sulphonamides, can be added in an amount of up to 10% by weight, based on the preparation.
Examples of further additives are inorganic and organic bases and also additives customary for pigment preparation.
Suitable bases are alkali metal hydroxides, for example NaOH or KOH, organic amines such as alkylamines, especially alkanolamines or alkylalkanolamines.
Particular preference is given to methylamine, dimethylamine, trimethylamine, ethanolamine, n-propanolamine, n-butanolamine, diethanolamine, triethanolamine, methylethanolamine or dimethylethanolamine.
Examples of suitable carboxamides and sulphonamides are urea and substituted ureas such as phenylurea, dodecylurea and others; heterocycles such as barbituric acid, benzimidazolone, benzimidazolone-5-sulphonic acid, 2,3-dihydroxyquinoxaline, 2,3-dihydroxyquinoxaline-6-sulphonic acid, carbazole, carbazole-3,6-disulphonic acid, 2-hydroxyquinoline, 2,4-dihydroxyquinoline, caprolactam, melamine, 6-phenyl-1,3,5-triazine-2,4-diamine, 6-methyl-1,3,5-triazine-2,4-diamine, cyanuric acid.
The base is optionally present in up to an amount of 20% by weight, preferably up to 10% by weight, based on the pigment.
But it is particularly preferable for the preparation of the invention to contain more than 90%, especially more than 95%, preferably more than 97%, by weight of pigment according to the invention, dispersant and optionally base.
The invention further provides a process for preparing the pigment preparation of the invention, characterized in that pigment and dispersant and optionally further additives are mixed.
The metal complexes of the invention are very useful for all pigment applications. They are useful for example for pigmenting varnishes of all kinds for the production of printing colours, distemper colours or binder colours, for the mass coloration of synthetic, semisynthetic or natural macromolecular substances, especially polyvinyl chloride, polystyrene, polyamide, polyethylene or polypropylene. They are also useful for the spin-dyeing of natural, regenerated or artificial fibres, for example cellulose, polyester, polycarbonate, polyacrylonitrile or polyamide fibres, and also for printing textiles and paper. These pigments provide finely divided, stable, aqueous pigmentations of emulsion and paint colours which are useful for paper coloration, for the pigment printing of textiles, for laminating and also for the spin-dyeing of viscose, by grinding or kneading in the presence of non-ionic, anionic or cationic surfactants.